The present invention relates to bisabolene isomer mixtures containing, but not limited to, compounds defined according to the structure: ##STR1## including the compounds having the structures: ##STR2## and uses of such mixtures in augmenting or enhancing the aroma of perfume compositions, perfumed articles and colognes; as well as uses thereof in repelling insects including Musca domestica L.(Diptera Muscidae) and Aedes aegypti.
The compositions of our invention are prepared by dehydrating nerolidol using citric acid or phosphoric acid dehydrating agents. Nerolidol isomers are defined according to the structure: ##STR3## and include cis and trans isomers thereof shown by the structures: ##STR4##
There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) fragrances to (or in) various consumable materials. The substances are used to diminish the use of natural materials, some of which may be in short supply and to provide more uniform properties in the finished product.
Natural, dry, floral, opoponax aromas with floral, freesia, fruity, citrus, bergamot, mango and opoponax topnotes are particularly desirable in several types of perfume compositions, perfumed articles and colognes, including "ginger" perfumes.
Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)", Volume I, at monograph 348 indicates that gamma bisabolene having the structure: ##STR5## has a pleasant, warm, sweet spicy, balsamic aroma inevitably reminding the perfumer of opoponax and "oriental" fragrance types. Arctander further states that gamma bisabolene finds good use in artificial oils of bergamot, myrrh, lemon and the like. Arctander further states that it may be produced from nerolidol "by dehydration".
Furthermore, Ruzicka and Capato, Helv. Chim. Acta 8, 259(1925) indicates that nerolidol having the structure: ##STR6## can be dehydrated to using formic acid to produce alpha bisabolene having the structure: ##STR7## beta bisabolene having the structure: ##STR8## and gamma bisabolene having the structure: ##STR9## as well as bisabolol having the structure: ##STR10##
However, Ruzicka and Capato and for that matter, any other relevant prior art do not disclose the use of citric acid or phosphoric acid to dehydrate nerolidol or natural materials containing nerolidol in large quantities such as Cabreuva oil to produce the novel composition of matter of our invention which has unexpected, unobvious and advantageous properties not only insofar as its organoleptic character is concerned but also regarding its character as a semio chemical; that is, in order to repel the insects, Musca domestica L.(Diptera Muscidae) as well as Aedes aegypti. Reference to Cabreuva oil as containing a large amount of nerolidol is set forth at columns 108 and 109 of "Perfume and Flavor Materials of Natural Origin", Arctander, 1960.
Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)", at Monograph 1378, discloses "Farnesal", 2,6,10-trimethyl-2,6,10-dodecatrien-12-al to have a very mild, sweet oily, slightly woody, tenacious odor. On the other hand, Arctander also describes, at Monograph 1379, Farnesene, 2,6,10-trimethyl-2,6,9,11-dodecatetraene defined according to the structure: ##STR11## to have a very mild, sweet and warm, rather nondescript odor of good tenacity. Arctander further states that apart from some possible use in the reconstruction of certain essential oils, there is to the author's knowledge, very little, if any, use for this sesquiterpene in perfumery as such. Arctander further states that Farnesene having the structure: ##STR12## is produced by dehydration of Farnesol by heat with a potassium dehydrating agent or from Nerolidol by heat with acetic anhydride.
Brieger, et al, J. Org. Chem., Volume 34, No. 12, December, 1969, in their paper "The Synthesis of trans,trans-alpha Farnesene" discloses dehydration of nerolidol using bisulfate at 170.degree. C. to yield a number of Farnesene isomers according to the reaction: ##STR13## Brieger, et al also discloses the dehydration of Farnesol using potassium bisulfate at 170.degree. C. as follows: ##STR14## Brieger also teaches the dehydration of Farnesol using potassium hydroxide at 210.degree. C. to yield certain isomers according to the following reaction: ##STR15##
Anet, Aust. J. Chem., 1970, 23, 2101-8, in a paper entitled "Synethesis of (E,Z)-alpha-, (Z,Z)-alpha-, and (Z)-.beta.-Faranesene" discloses the dehydration of (E)-nerolidol having the structure: ##STR16## in the presence of such dehydrating agents as phosphoryl chloride in pysridene to yield the compounds having the structures: ##STR17## according to the reaction: ##STR18##
In a paper by Hattori, et al entitled "Chemical Composition of the Absolute from Gardenia Flower" and in another paper by Tsuneya, et al entitled "GC-MS Analysis of Gardenia Flower Volatiles", it is disclosed that alpha-farnesene is existent in gardenia flower absolute. The Hattori, et al and Tsuneya, et al papers are published in the "VII International Congress of Essential Oils; Japan Flavor and Fragrance Manufacturers' Association, Tokyo (1979) at pages 451 and 454, respectively (papers 128 and 129, respectively).
Beroza, "Materials Tested As Insect Attractants", Agriculture Handbook No. 239, Agricultural Research Service, United States Department of Agriculture, June, 1963, at Table 2, discloses the use of certain hydrocarbons as insect attractants. Thus, Item No. 24 is 3-(1-butenyl)-2,4,4-trimethyl cyclohexene and is shown to be an attractant for the Oriental fruit fly, the Mediterranean fruit fly and the Mexican fruit fly as well as the Gypsy Moth and the Boll Weevil at levels of "1" on a scale of 1-3 and at a level of "2" for the Pink Bollworm. This compound has the structure: ##STR19## Beta phellandrene is also shown by Beroza, et al to be an attractant for the Oriental fruit fly at a level of "3" on a scale of 1-3 and an attractant for the Mediterranean fruit fly at a level of "1" on a scale of 1-3. Beta phellandrene is indicated as Item No. 56, in Table 2 of the Beroza reference. Beta phellandrene has the structure: ##STR20##
No structures remotely resembling the structure of any of the bisabolene isomers of our invention is shown to be a repellent or for that matter is shown to have any activity towards insects in the prior art. Furthermore, nothing in the prior art indicates the unexpected, unobvious and advantageous perfumery property of the composition of matter defined according to our invention. Accordingly, not only does the composition of matter defined according to our invention have valuable organoleptic properties from a perfumery standpoint but said composition also has valuable properties insofar as its insect repellency is concerned with regard to Musca Domestica L.(Diptera Muscidae) and Aedes aegypti. Interestingly, the composition of matter of our invention in addition has properties as a flavorant also.